Creep resistant structural element subject to high temperature in use



Sept. 26, 1939. a. M. WISE Er AL 2,174,025

CREE? RESISTANT STRUCTURAL ELEMENT SUBJECT TO HIGH TEMPERATURE IN USE Filed Jan 6, 1938 2 Shuts-Sheet 1 wmswyouks N INVENTORS 7; u/ ssyom-umswazx; 7:14am EDMUND M. W/SE y avq/wss 7.- sow ATTORNEY.

Sept. 26, 1939. EM. wlss'rr AL 2,174,025 CREE? RESISTANT STRUCTURAL ELEMENTSUBJECT TO HIGH TEMPERATURE IN USE 2 Sheets-Sheet 2 Fj le d Jan. 6, 1938 INVENTORS 6'5. BY JED IE5 TGOVY EDMUND M. W/

"-ATTORNEY.

Patented Sept. 2 1939 UNITED sTATEs arwqzs y v RUCTIIRAL ELEMENT or -.T0 HIGH TEMPERATURE IN;

CREE! RESISTANT ST SUBJE USE Edmund M. Wise, Westfleld,N. 1., and JamiesTi Ohio, assitnors to The Inter OompanyJnc a corporation ot'Delaware Application January 6, i938, ScrialNm 183,586 G'Giaim's; (01."148- -3-1) Gow, Columbus, national Nickel high temperatures, as in furnaces and the like.

Itis now well known that metals and alloys under prolonged stress at elevated temperatures flow or deform permanently and that such flow or deformation occurs under stresses far below those which can be sustained for short periods ot time. This fiow or deformation is called creepand the resistance to creep is definedas creep strength. Creep strength is usually expressed in terms of the stress required to produce agiven [rate of creep such as 1% or 0.1% in 1000 hours.

In, determining the creep strengths of alloys,- it is usual to apply a fixed load to aspecimen which is held at a constant, temperature-in a-furnace, to measure and record the increase'in length ,of the specimen at appropriate intervals and to plot the elongation against time to yield timeelongation curves. If the observations are carried out for a sufliciently long time, these curves can be divided into three-sections, determined by the slope of the elongation-time curve, corresponding to the three stages of creep. The first stage, in which the rate of elongation is decreas-' ing, is that made up of the elastic plus plastic flow. The second stage, in which the rate of elongation and the rate of creep remain sensibly constant, is generally the basis for design calculations and exterpolation to indicate the service life.- The total time of thefirst and second stages is also important in indicating service life and is defined as the time to inflection. In the third stage the rate of elongation is increasing and will continueto' increase until fracture occurs causing failure of the element.

In recent years the art has been earnestly endeavoring to obtain creep resistant structural elements made of heat resisting alloys, 1. e.', elements made of alloys with lower rates of creep at elevated temperatures and useful working stresses; The need for creep resistant load supporting elements is especially great in apparatus used by industries where processing involves high-tern peratures such as the heating and heat treatmeat of metals; the manufacture of Portland ce-- oil and the like.

- It was found, however, that 1 .iect, to a; peculiarltype' of ing been-heated within theapproximateltempe ,cinity-th e'reot; so that.-

them to establish that PATENT New-York, NrY.

ment, lass; chemicals and-pigments; refiningof] Early investigators Iound thatt-he short time-Z high temperaturecreepstrength of steels: was increased; by 'the addition of certainalloying ele- 5 ments. For example, molybdenum andtungsten were ffound to increase theshort time high-temperature strength" of low alloy'steels but unfor tunately these additions do-=not materially im prove the long: time creep strength.

Austen'itic chromium-hiekel'steels haveco'me' into wideiavor particularly in the chemicalfin dustrles because of their resistance to-"c'o'rr'o'sloh even at temperatures aboveroom, temperature; C

thesesteelswere;stilti disintegration ;ii'tlieyl conditions after" havwere exposed to corrosive tlire'range'of- 800"to 16001; for exitfiible, by welding, or in use atrather moderately elevated w temperatures but not at=highertemperaturesisiich:'-

as 1800 F. The grains of metal would still-be bright and apparentlyuncorroded while; the in tergranular material'wouidbeeaten away. Con-= siderable research in to the causes. and means of' A5 preventing this phenomenon, known as'intebgranular corrosion, wasprovoked; The results of this research haveled most investigators to the theory that the cause lies: in the formation l and precipitation of chromium carbides' at, the grain boundaries with resultant chromiumi i'inj poverishment or the matrixinthe' immediate vi when the" metal isexposed to strong corrodants the material neanthe-grain boundaries iseaten'awayJ The id'eal condition," so far as prevention of ihteiggranular corrosion is concerned, would therefore'be aicarbonicontent not in excess oi the amount the alloy come stain in' solid solution. The -exp'erinientsot' B'ain and his co-workers have: been" interpreted by in 18% chromium, 8% nickel-type. steels the maximum amountofcar bon that can be safely used does notexceed about 0.02%, as reported in Transactions of the Ameri 4& can Society for Steel'T'reat'ing, vol. XXI:(1933'), 1 pages 481 to -509. Under pr'esentl commercialpractice on an industrial scale it is-impracticabk; I however, to manufacture steels of this' type with such-a low carbon content.- 'I'hear't'was ac'coid'- g ingly compelled to-look to'some-other expedient- 1 (1934), pages 143 g 150-*which show munity to "disintegration to about ,15%-'-carbon. This is slight-lyin excess 'jratioi's necessary isex'plained' on page 507.0f thesaid article by Bain. r i

research intothe causes and means of preventingintergranular-corrosion did not assist in giyen onjpa ges 502 for a commercially practicable solution of this problem which was of particular importance in wrought rather than cast alloys. Among the proposed solutions was the addition of carbide forming elements such as tungsten, molybdenum, titanium, columbium, tantalum, etc., to austenitic chromium-nickel steels having as low a carbon content as it was practicable to produce. These carbide forming elements, if added in amounts at least equal to the; stoichiometric proportions for combining with all the carbon, are supposed to prevent the formation and therefore the precipitation of chromium boundaries. The importance of properly proportioning columbium, as an example of these elements, to the carbon, and of keeping the latter relatively low, 1. e., about 0.15% or less, in order to prevent intergranular 'corrosionin austenitic chromium-nickel steels is discussed in an article on Effect of Columbiurn in Chromium- Nickel Steels by Becket 8: Franks published in the Transactions of the American Institute ofv Mining and Metallurgical Engineers, vol.. 113 to 162. Data are given on page that a ratio of columbium to carbon of about 1011 is necessary to provide imin steels containing up or] 'the fstoichiometric' ratio for forming CbC (93:3:12 or 7,811); 'Similar data for titanium are to 508 otBains article referred to "above, "showing that a ratioof-about sins-necess ry whereas the stoichiometric' ratio for forming-flit) is about kl-(47.9212). The reason why 'slight excess over the stoichiometric anyway toward a'solution of the problem of incr'easingthe creep strength of structural elements :i-to high temperatures "case wit-h "furnace structural elements-rolls for 45,

mentfs'ubject to high temperature in use which are exposed during use,-such as is the made of heat resistant alloys glass'making;'-tubes used in the distillation and cracking of oil and various other high temperature uses, especially those of the chemical and 'metallurgical industries. Many attempts have been made to solve the outstanding problem of providing the art with a creep resistant structural element, especially a load-supporting eleand to satisfy the need of such elements, but, as far as "we are aware, none has trial scale.

been wholly successful, especially when' carried into practice on an indusf We have discovered that a creep resistant load supporting element made of austenitic chromiumnickel-'iron columbium alloys solves the problem confronting the art.

It isan'cbject'of the present invention toprovide a load supportingelement made of chro- ':""rnium-nickehiron columbium alloy having a spe- 'cial carboncontent which possesses not only superior creep strength but also possesses heat 4 resistance even-"at elevated temperatures up to It is a fur 85' load I supportingaboutlBOOF.

' 'ther' object of the invention to prov member made of an ausfienitic ,ch romium '-nickel-iron-columbium alloy temperatures as'a' 'result'of which the structural ,member may have a" smaller cross section and stilhposs'e's's thesai'ne strength as conventional structural members having a larger cross ection carbides at the grain and constituted cf prior in the amount of metal etc. may be efiected.

It is also within the contemplation of the invention to provide a load supporting element made of a columbium-containing austenitic chromiumnickel-iron alloy having a special carbon content and having a relatively high creep strength and a fine grain structure with finely distributed carbides,

Other objects and advantages of the invention will become apparent from the following description taken in conjunction with the accompanying drawings in which:

Fig. 1 illustrates a graph of time-elongation curves of a prior art alloy free from columbium (curve A) and an austenitic chromium-nickeliron alloy containing columbium and carbon within critical limits which are used in conjunction v with the present invention (curve B) furnace bound with buckstays and tie rods con- .structed in accordance with the principles of the present invention; and

Fig. 6 shows a side view of a tube support for oil still tubes cast from a nickel-chromiumcolumbium- -iron alloy of the present invention.

Generally speaking, the load supporting elements according to the present invention are made ofan improved heat resisting austenitic chromium nickel iron alloy containing special amounts of columbium and of carbon, varying from about 0.5 to about 5% and about 0.25% to about 0.75%, respectively.

An austenitic chromium-nickel-iron alloy will be understood by those skilled in the art to mean an alloy which is essentially a solid solution possessing a face centered cubic structure both at high temperatures and after cooling to low temperatures at ordinary rates. Nickel is primarily responsible for the production of this desirable austenitic structure, while the nickel and chromium jointly contribute to the resistance to oxidation. More specifically austenitic alloys, containing about 10 to 30% chromium, about 8 to 50% nickel and the balance essentially iron, are employed for making load supporting elements according to the present invention. For certain purposes the nickel content may exceed 50%, for example, very satisfactory glass forming rolls may be made containing about 65% nickel. Other elements in minor amounts such as manganese, silicon, etc., which may normally be present in commercial alloys, map be present without appreciably modifying the characteristics of the alloy or departing from the scope of the present invention and it is to be understood that such elements all iron.

' We have discovered that a carbon content within the special range of about 0.25 to 0.75% has provided highly satisfactory results whenused in conjunction with a special content of columbium in austenitic chromium-nickel-iron alloys and new results have been achieved with respect to creep strength. However, it was found that even in low carbon alloys tested at 1800 F. and

with a stress of 1000 pounds per square inch the second stage of creep decreased from 00077 per hour for the columbiupi free alloy to .00001% per hour for an alloycon'taining about 2.5% columbium and about .06% carbon. The creep rate of the columbium alloy at a stress of 2000 pounds per square inch was even lower than that of the columbium 'free alloy at a stress of 1000 pounds per square inch as is shown in Schedule I.

SCHEDIILE I Effect of columbium on the creep rate of low carbon alloys in the cast and annealed condition Second stage creep rate percent per hour at 1800 F. Alloy No. Cr Ni O Cb Fe Stress Stress 1000 psi 2000psi 1 "25.942017 .06 o Bal. .00077 2 .2e 2o .06 2.5 B81. .00001 .00024 It is well known that the addition of carbon within limits to a chromium-nickel-iron heat resisting alloy improves its creep strength and we have discovered that the further addition of columbium to ,these carbon containing alloys gives new results and still further improves the iron. It will be noted that the second stage creep rate of the new columbium-containing alloy (.00007%/hr.) is about one hundred-percent better than that of the old columbium-free alloy (.000l5%/hr.) with respect to creep strength. It will also be noted that the columbium-containing alloy required about 1366 hours to reach a point of inflection (beginning of rapid increasing'creep rate) which is' about .twice the time (about 690 hours) required by the columbiumfree alloy. Thus, it will be seen that the columbium-containing alloy will have at least twice the useful life in high temperature service that a columbium-free alloy would have.

We have discovered that even small additions of columbium of the order of improve the creep strength, but for marked improvement in creep strength, 1% or more of the columbium is required. The upper limit is about 5% but for most applications about 3% is a preferred maximum columbium content. Typical results are given in Schedule II.

the

'tion of 500 diameters.

SCHEDULE II Effect of columbium on creep rates of carboncontaining alloys tested in the cast and annealed condition Second stage creep rate percent per hourat 1800 F. Alloy No. Cr Ni O Ob Fe Stress Stress 2000psi 3000psi 25.40 20.52 0.37 0 Hal. ,000089 .00015 20 0.39 0.54 Bal. .000035 26 20 0.41 1.21 1331. .000008' .000062 .26 20 0.33 2.54 E31. .000004 .000067 carbon-containing heat resisting alloys favorably changed the structure'of these alloys yielding a better product. The micro-structure of the columbiumfreealloys containing carbon, as clearly seen in Fig. 2, reveals an austenitic matrix with massive carbides segregated immediately adjacent to the grain boundry carbides; In service at high temperature these Iine carbides agglomerate' into We found that the additionoi columbiurn to 'chromium-nickel-iron coarse carbides which merge with the original massive carbides. These movements are likely to produce localized volume changes distorting I the surface of the alloy. Fig.2 is a photomicrograph otalloy No'. 3 of Schedule II in the cast and annealed condition, taken at a magnifica- In contrast, the microstructure ofthe columbium-containing alloy, as

seen in Fig.3, reveals only the fine carbides and these are relatively stable as they do not agglomerate to the same extent as the fine carbides of the columbium-free alloy. Fig. -3 is a photomicrogra-ph of alloy No. 6 of Schedule II, also in the cast and annealed condition and taken at amagnification of 500 diameters This. superiority oithe columbium-containing alloy is pecially importantin certainv applications for resisting alloys, such as glass forming rolls, where the roll must be capable ofv taking and of maintaining a good polished surface which will, not mark the glass. H

Although most of the data presented {here relates to 'columbium containing chromiumniokel-iron alloys of the 26% chromium, 20% nickel type which are particularly useful in heat and corrosion resistant applications where substantial amounts of sulphur are present, many applications require alloys'with different chro-. .mium and nickel contents. We have discovered that the addition of columbium to other austenitic chromium-nickel-iron base compositions similarly ,improves the creep strength. Thus, at

about 1800 F. the results shown in Schedule III were obtained on high nickel content alloys.

SCHEDULE III Efle'ct on columbium on creep rates of high nickel alloys in the cast and annealed condition Second stage creep rate percent per hour M1800 F.

Alloy No. Or Ni 0 Ch Fe Stress Stress 2000 psi 3000psi 7 22.83 4232 .35 0 Hal. .ooozc .0019 8 22.50 42 .35 2.5 Bel. .000005 .0()()79 It will again be observed that columbium eat I 5 provements present invention,

markedly improves the creep strength of the austenitic chromium-nickel-iron heat resisting We-have further discovered that similar imin creep'strengths'may be obtained by the addition ,of columbium to austenitic. chromium-nickel-iron heat resisting alloys generally.

-By controlling the chromium and nickel content 'of the columbium-containing alloy of the the improved alloy maybe madev topo'ssess a wide range of useful properties as will be well understood by thoseskilled In producing the new alloy, we prefer to follow the conventional furnacing methods for producing.chromium-niclcel-iron alloys with the additional provision that the requisite quantity of columbium is added preferably late in the melting period .to minimize losses of this rather ex- 20 pensive element; The columbium may be added asflpurelcolumbium, .but is preferably added as the less expensive commercially available :ferrocolumbium, whicn'm'ayfalso contain some tan taluni.

g IThe alloys used for makingftheload supportmg eieme ts of the present invention should not beconfus'ed' with 'the above mentioned chromium-nickel-iron alloys to which modifying elements, such. as columbium; tantalum, titanium,

3o tiirig'steh','.molybdenum. etc., are added to' low arbonau'ey to reduce the susceptibility to intergra'nular attack, by chemicals and brittleness resulting. from .he'ating during welding. While .col "mum. is effective iiij'raising";the"creep r t 1f ngth bf bothf hig'h and low carbon alloys, the

* best results are. obtained o'n'the highcarbonalloys which isflthedirect opposite'towhat was found in thejinventlonsreferred to above.

In Figs. 4 and1g5 are illustratedspe'cific em- ;49 bcdiment's'of loadsupporting elements in con- 50 themQfrom .which understand. that the J temperature."

ll appreciable elongation.

yention'al metallurgical furnaces which are constructediin' accordance with the invention from nickel chromium-iron-columbium' alloys. The iiurnaceof Fig. ,4 has a'wide continuous hearth uflnwith a plurality of "arches? over it. The

. r d ,9 I are subjected'in "to' elevated tempera- \tures -and. heavy loads due to the expansion of the refractories ,in' I the arches with increasing By making them of nickel-chromium-iron-columbiuni alloys in accordance with the principles of .the present invention the useful life of these load supporting elements is greatly' extended. I

.55 Fig."5 illustrates asimilar application of tie rods made in accordance'with the present disclosu'redn a single arch furnace with a solid hearth l0 resting on a solid foundation I l. Buckstays l2, bottom tie rods l3-and top tie rods l4 =70 constitute the furnace binding. Because the solid 'h'eartnand solid foundation leave no cool place for the bottom tie rod l3, it mustwith'stand prolonged exposure to high temperature and stress set up by the expansion of the hearth without .Tie rods made of nickelchromium-iron alloys of the 26% chromium,

% nickel type with about .40% carbon and l to 3% columbium are eminently satisfactory for.

such purposes.

A tube support for oil still tubes such as that shown in Fig. 6 is an example of.a structure which is advantageously formed by casting the alloys of the 26% chromium, 20% nickel type having about .40 to .'75% carbon and from about 1 to about 3% of columbium. The tube support shown is of conventional design so far as shape is concerned, having shoulders 20 adapted to rest on supporting structures in the furnace, a

- web'2l having flanged openings 22 to receive the oil still tubes and reinforcing flanges 23 to strengthen and rigidity the support. When cast of the columbium containing alloys of the present invention, however, it may be made of lighter sections yet still have creep strength superior to prior art tube supports.

Similar results have been obtained with alloys having even higher nickel contents. ample, glass forming rolls containing about 65% nickel, about 15% chromium, about 0.75% carbon, about 1' to 5% columbium and the balance essentially iron were found to have not only high creep strength 'but to take and maintain a good polished surface in operation, probably traceable to the stability of the structure even at the elevated temperatures encountered in service.

It is to be observed that the present invention provides a load supporting element made of an improved columbium containing chromiumnickel iron heat resisting alloy containing special. amounts of columbiumand carbon with a superior creepstren'gth. It is' further to be noted that this invention provides a load supporting element made of an improved columbium containing chromiumnickeliron heat resisting alloy containing special amounts of columbium and carbon which is especially suited for-heat resistant purposes.

Furthermore, it is to be observed that the present invention provides an improved columbiumcontaining chromium-nickel-iron heat resisting alloy which is especially suited for use as load bearing structural members in high temperature service Moreover, it is to be noted that the load supporting structural elements of the present inventhan have a superior creep strength which permits the use of thinner sections whereby equipment having lighter weight but the same strength as conventional equipment may be employed thereby saving metal and heat.

It is also of importancethat the casting prop- 'ertiesare not impaired by columbium whereas aluminum, titanium, and the like, cause difficulties inxthe practical .production of castings in the foundry due to their tendency to form oxide skins on the metal.

It is likewise to be noted that the present invention provides structural elements made of an columbium containing chromium nickel-iron heat resisting alloy having a supecarbides, probably containing both chromium and columbium which, besides increasing the strength,

' aids in obtaining and maintaining the smooth 65 rior fine grain structure with finely distributed from the spirit and scope of the invention. Thus, when the term load supporting element or "structural element is used, it includessuch members as oil still tubes and tube supports, furnace parts, such as hearths, conveying rollers, work supports, heating element supports, enameling racks, carburizing boxes, frame work, etc., glass forming rolls and other elements subject to stress at high temperatures. Similarly, when psi is used, it means pounds per square inch". Likewise the term balance essentially all iron means that the alloy has substantially. those creep characteristics whichwould obtain if the balance were all iron, but it does not exclude impurities that are normally present in commercial alloys as will be understood by those skilled in the art.

Further, when the term improved creep rate in the second stage less than 0.00024% per hour is used in the claims it refers to the creep rate for a base or standard composition of 26% chromium, 20% nickel, 0.06% carbon, and 2.5% coiumbium. As will be apparent from the speci-' fication, and particularly Schedules I, II and III, the creep rate will vary with the composition and the stress, but will always be smaller for the co-- lumbium-containing composition than for a similar columbium-free composition. It will alsobe apparent to those skilled in the art that the creep rate is dependent upon the temperature to which the articles are subjected. Likewise, when the term improved creep strength at leas 100% better than one madeof a similar alloy tree from' columbium" is used, itreiers to thelsecond stage creep strength for a base or standard composition of 26% chromium, 20% nickel, 0.4% carbon, and 2.5% columbium under a stress of 3000 psi at a temperature of 1800 1. and will vary with the composition, stress and temperature.

We claim:

1. As an article of manufacture, a creep-resistant, load supporting element subject to high temperature in use and made of a creep and heat resistant austenitic chromium-nickeliron alloy characterized by a structure having an austenitic matrix and relatively stable flne carbides distributed in the grains, said alloy comprising 10 to 30% chromium, 8 to nickel, 0.25 to 0.75% carbon, 0.5% to 3% columbiuifn, and the balance essentially all iron, said load supporting element having an improved creep rate in the second stage less than 0.00024% per hour under a stress of 2000 pounds per square inch at 1800" F.

2. As an article of manufacture, a creep-resistant, load-supporting element subject to high temperatures in use and made of a creep and heat resistant iron-nickei-chromium alloy having an austenitic matrix and comprising 10% to 30% chromium,,8% to nickel, 0.06% to 0.75% carcoiumbium.

bon, 0.5% to 5% columbium, and the balance essentially all iron, said load supporting element having an improved creep strength at least 100% better than one made of a similar alloy free from coiumbium.

3. As an article of manufacture, a creep-resistant, cast structural element subjected in use to stress at elevated temperatures and constituted of a creep and heat resistant austenitic chromiumnickel-iron alloy characterized by a structure having an austenitic matrix and relatively stable fine carbides distributed in the grains, said alloy comprising 26% chromium, 20% nickel, 0.25 to 0.75% carbon, 1% to 3% columbium, and the balance essentialy all iron, said cast structural ele- ,ment having an improved creep rate in the second stage less than 0.00024% per hour under a stress of 2000 pounds per square inch at 1800 F.

4. As an article of manufacture, a creep resistant, cast, structural element subjected in use to stress at elevated temperatures and constituted of a creep and heat resistant austenitic chromiumnickel-iron alloy characterized by a structure having an austenitic matrix and relatively stable fine carbides distributed in the grains, said alloy comprising 10 to 30% chromium, 8to 65% nickel, 0.25 to 0.75% carbon, 0.5 to 5% columbium, and the balance essentially all iron, said cast structural element having an improved creep strength at least 100% better than one made of a similar alloy free from columbium. v

5. As an article of manufacture, a creep-resistant, cast, oil still tube support made of a creep and heat resistant-austenitic chromium-nickeliron alloy characterized by a structure having an austenitic matrix and relatively stable fine carbides distributed in the grains, said alloy comprising 26% chromium, 20% nickel, 0.4% carbon, 0.5%'to 3% columbium, and the balance essening an improved creep rate in the second stage less than 0.00024% per hour under a stressof 2000 pounds per square inch at 1800 F. 6. As an article of manufacture, a creep-resistant oil stilltube support made of a creep and heat resistant austenitic. chromium-nickel-iron alloy characterized by a structure having an austenitic matrix and relatively stable fine carbides distributed in the grains, said alloy comprising 10 to 30% chromium, 8 to 50% nickel, 0.25 to 0.75% carbon, 0.5 to 3% columbium, and the balance essentially all iron, said oil still tube support having an improved creep rate at least better than one made of a similar alloy free from EDMUND M. WISE. JAMES T. GOW. 

